Electrocatalytic CO2 reduction (ECR) has emerged as one of the most promising strategies to alleviate the energy crisis and CO2 pollution, for which a wide variety of catalysts are under development. Metal‐organic frameworks (MOFs) with clear and designable structures are an excellent platform for ECR. Here, two isostructural N, O‐coordinated Zn‐MOFs, FJU‐126‐4F and FJU‐126‐CH3, based on terephthalic acid ligand with different groups (one is ‐4F, the other is ‐CH3) on the benzene ring, have been constructed for ECR catalysts. Significantly, the different functional groups make the performance difference of ECR. The maximum Faraday efficiency of formate (FEformate) for FJU‐126‐4F is 60.5% with the partial current density of formate (jformate) of ‐19.35 mA cm‐2 at ‐1.47 V, while the optimum FEformate of FJU‐126‐CH3 is 50.2% with the jformate of ‐10.04 mA cm‐2 at ‐1.57 V. The work provides insight into the rational design of MOF catalysts for ECR.
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